Amidothionophosphoric acid esters

ABSTRACT

Amidothionophosphonic acid ester compounds of the formula:   IN WHICH R is alkyl of from 1 to 6 carbon atoms or lower cycloalkyl; Y is hydrogen, halogen or alkyl or alkoxy of from 1 to 6 carbon atoms; and Z is nitro or cyano; ARE OUTSTANDINGLY EFFECTIVE AS HERBICIDES AND EXHIBIT PARTICULARLY SELECTIVE ACTION.

United States Patent [191 [Hi 3,882,202 Aya et al. May 6, 1975AMIDOTHIONOPHOSPHORlC ACID Primary Examinerl.orraine A. WeinbergerESTERS Assistant Examiner-Richard L. Raymond [75] Inventors: MasahiroAya; Shigeo Kishino; g gg Agent or Flrm Burgess Dmklage &

Nobuo Fukazawa; Toyohiko Kume, p g all of Tokyo, Japan [57] ABSTRACT[73] Assignee: Bayer Aktlengesellschafl,

Leverkusen Germany Amldothionophosphomc acid ester compounds of theformula: [22] Filed: Dec. 27, 1972 [21] Appl. N0.: 319,092 S Z I G1CH PO [30] Foreign Application Priority Data ec, 27, 197i Japan 46405444 RNH[52] [1.8. CI. 260/951; 7l/87; 260/940; in which 260/954 R is alkyl offrom 1 to 6 carbon atoms or lower [51) Int. Cl. C07! 9/40 cyclcalkyl;

0f Selll'flh Y hydrogen halogen or or alkoxy of from 1 to 6 carbonatoms; and Reierences Clted Z is nitro or cyano; FOREIGN PATENTS ORAPPLICATIONS are outstandingly effective as herbicides and exhibit179,3!7 5/1966 U,S,S.R 260/954 particularly selective action. 1,330,3485/l962 France A. 260/954 15 Claims, No Drawings AMIDOTHIONOPHOSPHORICACID ESTERS The present invention relates to certain newamidothionophosphonic acid ester compounds, to herbicidal compositionscontaining such compounds, and to their use as herbicides.

From the specification of U.S.S.R. Pat. No. 2l6,380 it is known that theamidothionophosphonic acid ester of the formula ico-U H N'H has aherbicidal activity.

The present invention provides amidothionophosphonic acid esters of thegeneral formula S Z Cm2\ Q I RNH Y in which R is alkyl of from I to 6carbon atoms or lower cycloalkyl;

Y is hydrogen, halogen or alkyl or alkoxy of from 1 to 6 carbon atoms;and

Z is nitro or cyano.

The compounds of the formula (1) exhibit an excellent herbicidalactivity.

R in formula (I) is preferably alkyl of from 1 to 4 carbon atoms (namelymethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl ortert.-butyl), cyclopentyl or cyclohexyl, while Y is preferably hydrogen,halogen (that is, fluorine, chlorine, bromine or iodine), alkyl of froml to 4 carbon atoms or alkoxy of from 1 to 4 carbon atoms (namelymethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxyor tertbutoxy). These compounds are preferred because of theirexceptional herbicidal activity and/or selectivity.

The compounds of this invention, as stated above, have excellentherbicidal activity. Their activity is superior to the herbicidalactivity shown by the compound described in U.S.S.R. Pat. No. 216,380,to which reference has been made above, or by other compounds havingstructural formulas similar to formula (I). In particular, when theactive compounds of this invention are applied to paddy-field weeds,they exhibit an excellent herbicidal activity against the grasses,broad-leafed weeds and perennial weeds without showing any phytotoxicityto rice plants.

The present invention also provides a process for the production of anamidothionophosphonic acid ester of the formula (I) in which a. a phenolof the general formula thereof, with a chloromethane thionophosphonamidechloride of the general formula ClCH or (b) a chloromethanethionophosphonyl chloride of the general formula is reacted (optionallyin the presence of an acidbinding agent) with an amine of the generalformula in which formulas R, Y and Z have the meanings stated above.Process variant (a) may be illustrated by the following formula scheme:

M is a hydrogen or an alkali metal (preferably sodium or potassium)atom.

Examples of the chloromethane thionophosphonamide chlorides of thegeneral formula (ll) are N- methyl-chloromethane thinophosphonamidechloride, N-ethyl-chloromethane thionophosphonamide chloride, Nn-(oriso-)propyl-chloromethane thionophosphonamide chloride, N-n-(or isoorsec.-)butylchloromethane thionophosphonamide chloride and Ncyclohexylchloromethane thionophosphonamide chloride.

Examples of the phenols of general formula (III) are 2-nitrophenol,2-cyanophenol, 2-nitro-4-methylphenol, Lcyano-4-methylphenol,2-nitro-4-ethylphenol, 2-nitro-4-tert.-butylphenol,2-nitro-4-chlorophenol, 2- cyano-4-chlorophenol, 2-nitro-4-bromophenol,and 2-nitro-4-rnethoxyphenol.

Process variant (b) may be illustrated by the following reaction scheme:

Examples of the chloromethane thionophosphonyl chlorides of the generalformula (IV) are -2- nitrophenyl-chloromethane thionophosphonylchloride, 0-2-cyanophenyl-chloromethane thionophospho nyl chloride.0-(2-nitro-4-methylphenyl)- chloromethane thionophosphonyl chloride,0-(2- cyano-4-methylphenyl)-chloromethane thionophosphonyl chloride,O-(2-nitro-4-ethylphenyl)- chloromethane thionophosphonyl chloride,0-(2-nitro- 4-tert.-butylphenyl)-chloromethane thionophosphonylchloride, 0-(2-nitro-4-tert.-butylphenyl)- chloromethanethionophosphonyl chloride, 0-(2-nitro- 4-chlorophenyl)-chloromethanethionophosphonyl chloride, 0 (2-cyano-4-chlorophenyl)-chloromethanethionophosphonyl chloride, O-(2-nitro-4- bromophenyl)-chloromethanethionophosphonyl chloride, and O-(2-nitro-4-methoxyphenyl)-chloromethanethionophosphonyl chloride.

Examples of the amines of the general formula (V) are methylamine,ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine,sec.- butylamine, cyclopentylamine and cyclohexylamine.

The synthesis of the active compounds according to either of the aboveprocess variants is preferably conducted in a solvent or diluent. Forthis purpose, practically any inert organic solvent or diluent may beused, especially aliphatic, alicyclic and aromatic hydrocarbons (whichmay be chlorinated), such as hexane, cyclohexane, petroleum ether,ligroin, benzene, toluene, xylenes, methylene chloride, chloroform,carbon tetra chloride, mono-, diand trichloroethylenes, andchlorobenzene; ethers, such as diethyl ether, methyl ethyl ether,di-isopropyl ether, dibutyl ether, ethylene oxide, dioxane andtetrahydrofuran; ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone and methyl isopropyl ketone; nitriles, such asacetonitrile, propionitrile and acrylonitrile; alcohols, such asmethanol, ethanol, isopropanol, butanol and ethylene glycol; esters,such as ethyl acetate and amyl acetate; acid amides, such as dimethylformamide and dimethyl acet amide; sulphoxicles and sulphones, such asdimethyl sulphoxide and sulphoran; and bases, such as pyridine. Watermay also be used for this purpose.

Either of the above process variants may involve the use of anacid-binding agent. For this purpose, there may be used any customaryacid-binder, such as a hydroxide, carbonate, bicarbonate or alcoholateof an alkali metal, or a tertiary amine, for example triethylamine.diethylaniline or pyridine. However, the reaction of process variant (a)may be effected in the absence of such an acid-binder by reacting ametal or ammonium salt of the appropriate phenol (III) with the chloromethane thionophosphonyl chloride, this method of working can give ahigh yield of the intended product having a high degree of purity.

In either of the above process variants, the reaction may be effected attemperatures within a wide range; generally, the reaction is carried outat from 20C to the boiling point of the reaction mixture, preferably atfrom 0C to 100C or to the boiling point of the reaction mixture,whichever is the lower.

The preparation of the compounds of this invention is illustrated by thefollowing preparative Examples.

EXAMPLE 1 Preparation of 0-(2-nitro4-methylphenyl )-N-isopropylchloromethane thionophosphonamide ester 15.3 g (0.1 mole) of2-nitro-4-methylphenol were dissolved in 100 ml of methyl ethyl ketone,and 14 g (O.l 1 mole) of potassium carbonate were added to the solution,which was then agitated at 50C for 30 minutes. At 30 35C, 20.6 g (0.1mole) of N-isopropyl chloromethane thionophosphonamide chloride wereadded dropwise to the solution. The reaction mixture was agitated at 5055C for 4 hours to complete the reaction. The methyl ethyl ketone wasremoved by distillation and I00 ml of benzene were added to the residue.The mixture was washed with water, with 2% aqueous potassium hydroxidesolution and again with water and dried over anhydrous sodium sulfate.Removal of the benzene by distillation gave 25 g (yield of0-(2-nitro-4-methylphenyl)-N-isopropyl chlo' romethanethionophosphonamide ester characterized by a refractive index n of1.5737. The product is hereinafter referred to as compound No. I; it hasthe following formula:

2 ClCH :1

2\ XL Compound 1 iso-C H NH EXAMPLE 2 Preparation of0-(2-nitro-4-rnethylphenyl)-N-cyclohexyl chloromethanethionophosphonamide ester 30 g (0.1 mole) of 0-(2-nitro-4-methylphenyl)-chloromethane thionophosphonyl chloride were dissolved in ml of benzene,and 19.8 g of cyclohexylamine Were added dropwise to the solution at5-l0C. The mixture was agitated at room temperature for 2 hours and thenat 35"40C for 2 hours, following which it was air-cooled, washed withwater, dilute (1%) hydrochloric acid, 2% aqueous potassium hydroxidesolution and again with water, and dried over anhydrous sodium sulfate.Distillation of the benzene gave 29 g (yield 82%) of0-(2-nitro-4-methylphenyl)-N- cyclohexyl chloromethanethionophosphonamide ester characterized by a refractive index n of1.5818. The product is hereinafter referred to as Compound No. 2 and hasthe following formula:

NO S 2 Compound (2) The compounds characterized in the following Tablewere prepared by methods analogous to those described above.

As disclosed hereinabove, the instant compounds exhibit markedherbicidal activity.

When the compounds of this invention are applied in small amounts toupland weeds, especially in the preemergence treatment thereof, theyexhibit an excellent selective herbicidal activity without showing anyphytotoxicity to the cultivated plants. In this regard, the compounds ofthe present invention are superior to many conventional herbicides.

When the compounds of this invention are used in large amounts (e.g.,5.0 40 kg per hectare calculated as active ingredient), they exhibit anon-selective herbicidal activity. However, when they are used in smallamounts (i.e., 1.0 5.0 kg per hectare), they exhibit an excellentselective herbicidal activity. For this reason, they can be used asgermination-preventing agents, especially as weed-controlling agents.The term weed" is used in its broadest sense in this specification toinclude all plants growing in places where their growth is not desired.

The active compounds according to the invention exhibit a herbicidalactivity against, for example, the following plants: dicotyledons, suchas cleavers (Galium), chickweed (Stellaria), chamomile (Matricaria),gallant soldier (Galinsoga), goosefoot (Chenopodium), annual nettle(Urtica), grounsel (Senecio), amaranth (Amaranthus) and common purslane(Portulaca); and monocotyledons, such as timoth (Phleum), bluegrass(Poa), fescue (Festuca), goosegrass (Eleusine), foxtail (Setaria),ryegrass (Lolium), fingergrass (Digitaria) and barnyard grass(Echinochloa). However, in small applied amounts, they show nophytotoxicity towards such dicotyledons as mustard (Sinapis), cress(Lepidium), cotton (Gossypium), beets (Beta), carrots (Daucus), beans(Phaseolus), cabbage (Brassica), potatoes (Solanum) and coffee (Coffea)and such monocotyledons as maize (Zea), rice (Oryza), oats (Avena),barley (Hordeum wheat (Triticum), millet (Panicum) and sugar cane(Saccharum).

The compounds of this invention, owing to their excellent biologicalactivities, can be used to increase production and to save labor inagriculture. They may therefore be used with advantage in agriculturalapplications.

The active compounds according to the present invention can be convertedinto the usual formulations, such as solutions, emulsions, suspensions,tablets, fumigants, aerosols, powders, pastes and granulates. These maybe produced in known manner, for example, by mixing the active compoundswith extenders, that is, liquid or solid or liquefied gaseous diluentsor carriers, optionally with the use of surface-active agents, that is,emulsifying agents and/or dispersing agents and/or foam-forming agents.In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatichydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes,chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes,ethylenechloride or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, or strongly polar solvents, such as dimethyl formamide,dimethyl sulfoxide or acetonitrile, as well as water.

By liquefied gaseous diluents or carriers are meant liquids which wouldbe gaseous at normal temperatures and pressures, for example aerosolpropellants, such as halogenated hydrocarbons, for example freon.

As solid diluents or carriers, there are preferably used ground naturalminerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, or ground synthetic minerals,such as highly-dispered silicic acid, alumina or silicates.

Preferred examples of emulsifying and foam-forming agents includenon-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acidesters, polyoxyethylenefatty alcohol ethers, for examplealkylarylpolyglycol ethers, alkyl sulfonates, alkyl sulfates and arylsulfonates as well as albumin hydrolyzation products; and preferredexamples of dispersing agents include lignin sulfite waste liquors andmethyl cellulose.

Possible adjuvants include organic matter, stabilizers, adhesive agents,for example soap, calcium, calcium caseinate sodium alginate, polyvinylalcohol, steeping agents, coumarone (or indene) resins or polyvinylbutyl ether, combustible materials (for fumigants), for examplenitrites, zinc dust or dicyandiamide, oxygenyielding substances, forexample perchlorates or dichromates, phytotoxicity-reducing substances,for example zinc sulfate, ferrous chloride or copper nitrate, substancesfor prolonging the biological effect, for example chlorinatedterphenyls, emulsion-stabilizin g substances, for example casein, gumtragacanth and carboxymethyl cellulose (polyvinyl alcohol also beingsuitable for this purpose), and synergistic agents.

The formulations contain, in general, from 0.1 to 95%, preferably from0.5 to by weight of the active compound.

The compounds of the present invention can, if desired, be applied withother agricultural chemicals such as insecticides, acaricides,nematiocides, antiviral agents, herbicides and plantgrowth regulators,as well as with fertilizers.

The ready-to-use preparations (which may be pre pared from suitableformulations by, for instance, dilution with water) may be applied ineither preemergence or post-emergence treatments in any usual manner,for instance, by spraying, such as liquid spraying, misting, atomizing,dusting, scattering, watering, pouring, fumigating. by soil application,such as mixing, sprinkling, vaporizing and irrigating, by surfaceapplication, such as painting, banding and dressing (dusteoating), or byimmersion.

The amount of the active compound in the ready-touse preparation isgenerally from 0.0001 20% by weight, preferably 0.005 by weight. Thequantity of the active ingredient can be varied according to the type ofpreparation used, the method, purpose, time and place of the applicationand the growth state of the weeds to be controlled.

The compounds to be used according to the present invention may be alsoused in accordance with the wellknown ultralow-volume (ULV) process.According to this method, it is possible to use a concentration of theactive ingredient of up to 95% by weight, or even to apply the activecompound alone.

The dosage per unit area is generally 3 to 1000 g, preferably 30 to 600g, by weight of active compound per 10 acres. However, it is possible toincrease or reduce the usual amount and, in special cases, it mayactually be necessary to do sov The present invention also provides aherbicidal composition containing as active ingredient a compound of thepresent invention in admixture with a solid or liquefied gaseous diluentor carrier or in admixture with a liquid diluent or carrier or inadmixture with a liquid diluent or carrier containing a surface activeagent.

The present invention also provides a method of combating weeds whichcomprises applying to the weeds or a weed habitat a compound of thepresent invention alone or in the form of a composition containing asactive ingredient a compound of the present invention in admixture witha diluent or carrier.

The present invention further provides methods of providing cropsprotected from damage by weeds by being grown in areas in whichimmediately prior to and/or during the time of the growing a compound ofthe present invention was applied alone or in admixture with a diluentor carrier. It will be seen that the usual methods of providing aharvested crop may be improved by the present invention.

The herbicidal compositions of this invention are illustrated by thefollowing Examples, in which the compounds of this invention areidentified by the numbers assigned to them in Examples 1 and 2 andTable 1. Parts are by weight.

EXAMPLE I (Wettable Powder) parts of Compound No. 8, 80 parts ofa 1:5mixture of diatomaeeous earth and kaolin and 5 parts of an emulsifier (apolyoxyethylene alkyl aryl ether) were ground and mixed together to forma wettable powder. It was diluted with water before being applied.

EXAMPLE ll (Emulsifiable Liquor) 30 parts of Compound No. l, 30 parts ofxylene, 30 parts of methylnaphthalene and 10 parts of an emulsitier (a)polyoxyethylene alkyl aryl ether were mixed by stirring to form anemulsifiable liquor. It was diluted with water and applied by spraying.

EXAMPLE Ill (Dust) 2 parts ofCompound No. 7 and 98 parts ofa 1:3 mixtureof talc and clay were ground and mixed together to form a dust. This wasapplied by scattering.

EXAMPLE IV (Dust) [.5 parts of Compound No. 5, 0.5 part of isopropylhydrogen phosphate (PAP) and 98 parts of a 1:3 mixture of talc and claywere ground and mixed together to form a dust. This was applied byscattering.

EXAMPLE V (Granules) 25 pars of water were added to a mixture of 10parts of Compound No. 2, l0 parts of bentonite, 78 parts of a l :3mixture of talk and clay and 2 parts oflignin sulfomate. The resultingmixture was intimately blended and finely divided by means of anextruding granulator to obtain granules of 20 40 mesh, which were driedat 40-SOC. The resulting granules were applied by spraying.

EXAMPLE Vl (Granules) parts of clay particles of a size distribution of0.2 2 mm were put into a rotary mixer and a solution of 5 parts ofCompound No. l0 in an organic solvent was sprayed onto the particlesbeing rotated, thereby wetting the particles homogeneously. They werethen dried at 40-50C to form coated granules, which were ap plied byspraying.

EXAMPLE Vll (Oil Preparation) 0.5 part of Compound No. 4, 20 parts ofmethylnaphthalene, and 79.5 parts of kerosene were mixed by stirring toform an oil preparationv It was applied by spraying.

Compared with active compounds of similar structures which have beendescribed in the literature of known compounds exhibiting a similardirection of activity, the compounds of this invention are characterizedby substantially improved effects and by a very low toxicity towarm-blooded animals. Accordingly, the compounds of this invention areof great utility.

The herbicidal activity of the compounds of this invention isillustrated in the following Examples in which the active compounds ofthis invention are identified by the number assigned to them in Examples1 and 2 and Table 1.

EXAMPLE A Test on effects against paddy-field weeds in a waterappliedpro-emergence treatment:

Preparation of Sample Formulation Solvent: 5 parts by weight of acetoneEmulsifier: 1 part by weight of benzyloxypolyglycol ether in order toprepare a suitable formulation of an active compound, one part by weightof the active compound was mixed with the above amount of the solventcontaining the above amount of the emulsifier, and the mixture wasdiluted with water to form an aqueous formulation containing the activecompound at a pre scribed concentration.

Test Procedure:

Wagner pots 1/5000 are) were charged with soil from a rice paddy field.Two seedlings of rice (Kinmaze variety) at the threeor four-leafed stage(about l5 cm were evaluated on respective scales of from to as shownbelow.

Herbicidal Effect Weed Killing Ratio in height) prior to tlllermg wereplanted in each pot. I I Seeds of barnyard grass, flat sedges andbroad-leafed Z 3S3; f gtg g weeds were sown, and the soil was infectedwith spike- 3 more tha 5 up w 30% rush and watered to a depth of 6 cm.The active com- 2 30% P 50% l more than up to pound in the form of anemulsion prepared in the above 10 0 10% or |55 (no w manner was appliedto the water in a prescribed amount Degree of PhytotoxicityPhytotoxicity Ratio After the chemical treatment, water was leaked from5 more than 90% (f l damage) each pot for two days in an amountcorresponding to 2 more tgan "P 10 32 2-3 cmdepth per day; thereafter,the depth of water 15 2 ig as 3 was maintained at about 3 cm. Four weeksafter the I) rlq0%dor less o amage chemical treatment, the herbicidal(weed controlling) The results am Show" in Table A effect and the degreeof phytotoxicity to the nee plants Table A Com- Active pound compoundNo. conccn- Hcrbicidul Effect Phylotutration Barn- Broad xicity (g/ltlyard Flat Spike lcavcd Rice are) grass sedge rush weeds plant I 300 5 55 5 0 I50 5 5 5 5 0 5 5 4 5 0 2 300 5 5 5 5 0 150 5 4 4 4-5 0 75 4 4 3 40 3 300 5 5 5 5 0 150 5 5 4 4 0 75 4 4 4 4 0 4 300 5 5 5 5 0 150 4-5 4 44 0 75 4 3 3 4 0 5 300 5 5 5 5 0 150 5 4 4 4 u 75 5 4 3 4 0 6 300 5 5 55 0 150 5 5 5 5 u 75 4 4 4 4 0 7 300 5 5 5 5 0 I50 5 5 4 5 u 75 5 4 44-5 0 s 300 5 5 5 5 0 I50 5 5 5 5 0 75 5 5 4 5 0 9 300 5 5 5 5 0 I50 4 44 4 0 75 4 3 3 3 0 I0 300 5 5 5 5 0 150 5 5 4 5 u 75 4 4 4 4-5 0 VI 3000 0 0 0 0 (comparison) l 50 0 0 0 0 0 75 0 0 0 0 0 vn 300 0 0 0 0 0(comparison) l 50 0 U 0 (J 0 75 0 0 0 0 0 VI" 300 0 0 0 0 0 (comparison)l 50 0 0 0 0 0 75 0 0 0 0 0 [X 300 4 3 1 3 0 (comparison l 50 2 l 0 2 075 0 0 0 0 0 x 300 4 3 2 3 0 (comparison) lit) 2 l 0 2 0 75 0 0 0 u o XIM 5 5 4 4 0 (comparison 500 2 2 0 (J 0 250 0 0 0 0 0 X]! 500 5 5 5 5 4(comparison) 250 5 5 4 5 3 2 4 u 3 1 Table A Continued Comparison (Vll)Comparison (Vlll) Comparison (lX) Comparison (X) Comparison (XI)Comparison (XII) 2,4-dichlorophcnyl4-nitrophcny| ether (commerciallyavailable product) pentachlorophcnol (commercially available product)(ii) Broad-leafed weeds include monochoria. Rotala indicu, falsepimpernol and Dopatrium junceumv EXAMPLE B to the pot to a depth ofabout 6 cm. The active com pound in the form of an emulsion prepared inthe manner described in Example A was applied in a prescribed amount.

After the chemical treatment, water was leaked from each pot for 2 daysin an amount corresponding to 2 3 cm depth per day, and thereafter thedepth of water was maintained at about 3 cm. Four weeks after thechemical treatment, the herbicidal (weed-controlling) effect and degreeof phytotoxicity towards the rice plants were evaluated on the scalesdescribed in Example A7 The results are shown in Table B.

Table B Compound No.

Active compound concentration (gilt) arc) Herhicidal EffectPhytotoxicity Rice plant Broadlcaved weeds Barnyard grass Spike- Sedgerush V! (comparison) Vll (comparison) Vlll (comparison) 1X (comparison)400 200 l 00 400 200 l 00 400 200 l ()0 400 200 l[)() 400 200 100 400200 100 400 200 l ()0 400 200 l 00 400 200 100 400 200 l ()0 400 200 l00 400 Compound No.

400 ZUO [U0 H100 500 250 500 250 125 X (comparison) X] (comparison) Xll(comparison) plants and to the weeds was evaluated on a scale from 0 to5 as shown below:

Degree of Damage 0: no influence 1: slight damage and slight growthretardation and, 24 hours later, the active compound in the form 2:considerable damage and considerable growth retardation 3: extremedamage and only of seeds germinated 4: only 25% of seeds germinated 5:complete extinction with no germination damage done to the upland riceand other cultivated 30 The results are shown in Table C.

Table C Degree of Damage Com- Polymon Flat gonum Goose- Cocks purs- Soysedge blumei foot foot lane Rice Radish Carrot Maize bean BarnyardFinger grass grass EX AM PLE C Active Compound compound No.concentration (g/IO are) Test on effects on various upland plants in apreemergence treatment.

Seeds of upland rice, other cultivated plants and weeds were sown insoil-charged pots (30 X 30 cm) Note:

The comparison compounds and broad-leafed weeds are as identified in thefootnotes to Tahlc A,

of an emulsion prepared as described in Example A was applied to thesoil surface in an amount (calculated as the active compound) of 500 g,250 g or 125 g per l0 ares. Three weeks after the chemical treatment,the

Table C Continued Active Degree of Damage Compound compound Com- No.conccn- Burn- Poly mon tration yard Finger Flat gonum (Joose- Cockspurs- Soy (g) 10 are) grass grass sedge blumci foot foot lane RiceRadish Carrot Maize beam Xl I000 5 S 5 4 5 5 5 3 4 1 3 2 (comparison)500 3 3 3 2 U 2 2 (1 (J U (1 250 U (I (J (J (J U U U U (l (1 Xll 500 5 55 5 S 5 5 5 5 5 5 {comparison} ZSll 5 5 5 5 5 5 5 2 U l (J 2 l 3 3 4 2 22 4 U U U 0 Xlll I50 5 5 5 5 5 5 5 4 5 3 4 [comparison] H11) "4 4 5 4 45 S 2 3 2 (l 2 SU 2 Z 4 4 4 4 4 l 2 l l l Note:

1:) Comparison XIII lchlnrn-{h-histcthy|uminu)-Slriannc (commcrcialluvmlnhlc product! Hi) The other comparison compounds are as identifiedin the footnotes to Table A.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:

l. Amidothionophosphonic acid ester compound of the formula:

5. Compound as claimed in claim 1 wherein Y is alkyl of from 1 to 4carbon atoms.

6. Compound as claimed in claim 1 wherein Y is alk oxy of from 1 to 4carbon atoms.

7. Compound as claimed in claim 1 wherein Y other than hydrogen and isin the 3-position.

8. Compound as claimed in claim 1 wherein Y other than hydrogen and isin the 4-positionv 9. Compound as claimed in claim 1 wherein Y otherthan hydrogen and is in the 5-position.

10. Compound as claimed in claim I wherein Y other than hydrogen and isin the 6-positionv 11. Compound as claimed in claim 1 wherein saidcompound is O-(2-nitro-4-methylphenyl)-N isopropyl chloromethanethionophosphonamide ester.

12. Compound as claimed in claim 1 wherein said compound is O-(2-nitro-4-methylphenyl)-N-cyclohexyl chloromethane thionophosphonamideester.

13. Compound as claimed in claim 1 designated 0-(2-nitro-4-methylpheny])-N-n-propyl chloromethane thionophosphonamideester.

14. Compound as claimed in claim I designatedO-(2-nitrophenyl)-N-isopropyl chloromethane thionophosphonamide ester.

15. Compound as claimed in claim 1 designated 0-(2-nitro-4-methoxyphenyl)-N-isopropyl chloromethane thionophosphonamideester.

1. AMIDOTHIONOPHOSPHONIC ACID ESTER COMPOUND OF THE FORMULA:
 2. Compoundas claimed in claim 1 wherein R is alkyl of from 1 to 6 carbon atoms. 3.Compound as claimed in claim 1 wherein Y is hydrogen.
 4. Compound asclaimed in claim 1 wherein Y is halogen.
 5. Compound as claimed in claim1 wherein Y is alkyl of from 1 to 4 carbon atoms.
 6. Compound as claimedin claim 1 wherein Y is alkoxy of from 1 to 4 carbon atoms.
 7. Compoundas claimed in claim 1 wherein Y is other than hydrogen and is in the3-position.
 8. Compound as claimed in claim 1 wherein Y is other thanhydrogen and is in the 4-position.
 9. Compound as claimed in claim 1wherein Y is other than hydrogen and is in the 5-position.
 10. Compoundas claimed in claim 1 wherein Y is other than hydrogen and is in the6-position.
 11. Compound as claimed in claim 1 wherein said compound is0-(2-nitro-4-methylphenyl)-N-isopropyl chloromethane thionophosphonamideester.
 12. Compound as claimed in claim 1 wherein said compound is0-(2-nitro-4-methylphenyl)-N-cyclohexyl chloromethanethionophosphonamide ester.
 13. Compound as claimed in claim 1 designaTed0-(2-nitro-4-methylphenyl)-N-n-propyl chloromethane thionophosphonamideester.
 14. Compound as claimed in claim 1 designated0-(2-nitrophenyl)-N-isopropyl chloromethane thionophosphonamide ester.15. Compound as claimed in claim 1 designated0-(2-nitro-4-methoxyphenyl)-N-isopropyl chloromethanethionophosphonamide ester.